Assessment of Agro-Industrial Wastes Proximate, …environmentaljournal.org/2-6/ujert-2-6-13.pdfand...

Universal Journal of Environmental Research and Technology

All Rights Reserved Euresian Publication © 2012 eISSN 2249 0256

Available Online at: www.environmentaljournal.org

Volume 2, Issue 6:575-581

Open Access Research Article

575

Veeresh and Narayana

Assessment of Agro-Industrial Wastes Proximate, Ultimate, SEM and FTIR analysis for

Feasibility of Solid Bio-Fuel Production

Santhebennur Jayappa Veeresh and Jogttappa Narayana

Department of P.G Studies & Research in Environmental Science, Bioscience Complex, Kuvempu University,

Shankaraghatta-577 451, Karnataka State, India

Corresponding author: [email protected]

Abstract: Disposal of biomass wastes, produced in different agro-industrial activities, is normally an environmental

problem. A key for such condition is the utilization of these residues for the production of energetic solid

bio-fuel by increasing their proximate and ultimate properties of biomass. The aim of the present study

agro-industrial wastes like press dug, saw mill dust, ground nut husk, jatropa seed cake, castor seed cake

and tamarind fruit shell were analyzed for the feasibility for production of bio-briquettes. Agro-industrial

wastes moisture content, bulk density, particle density, ash content, fixed carbon, calorific value, SEM and

FTRI analysis were done by using standard procedures. The results concluded that combination of raw

materials used during the production of bio-briquettes will give better mechanical and combustion

properties than single raw material used. The final disposal of biomass wastes from agricultural activities is

usually an environmental problem. Hence these agro-wastes utilized for production of briquettes turn out to

be an environmental friendly fuel that is relatively simple to use and reduces environmental pollution.

Keywords: biomass, briquette, combustion, renewable energy, sustainable agriculture, sludge

1.0 Introduction: Biomass as the solar energy stored in chemical

form in plant and animal materials is among the

most precious and versatile resources on earth.

The solar energy, which is stored in plants and

animals, or in the wastes that they produce, is

called biomass energy. This energy can be

recovered by burning biomass as a fuel (Tewfik,

2004). Biomass has considered as great potential

renewable energy source, both for the richer

countries and for the developing world (Demirbas,

2001). Biomass is the third largest primary energy

resource in the world, after coal and oil (Bapatet

al., 1997). In all its forms, biomass currently

provides about 1250 million tonnes of oil

equivalent (m tone) of primary energy which is

about 14% of the world’s annual energy

consumption (Wertheret al., 2000). The average

majority of biomass energy is produced from wood

and wood wastes (64%), followed by solid waste

(24%), agricultural waste (5%) and landfill gases

(5%) (Demirbas, 2000).

At present, briquetting is commonly used in

developing countries. The use of agricultural and

forest wastes as well as industrial by-products for

production of briquettes are increasing (Tabareset

al., 2000). It is relevant to the use of the briquettes

prepared with raw biomass and/or charcoal

(Pastor et al., 2001). Some of the workers worked

on the production of briquettes with out binder

from wood sawdust (Cheremisinoff, 1980), cotton

stalks (Abasaeed, 1992), straws of colza (Bartel,

1997). Briquetting of raw agricultural residues

without binder is more commonly practicing in

India (Tripathiet al.,, 1998). Few of the commonly

used agricultural residues for briquetting in India

include arhar stalk (Cajanuscajan), cotton stalk,

mustard stalk, maize stalk, groundnut shells, rice

husk, tamarind shells, coir pith, sun flower stalk,

etc. (Tripathiet al., 1998). Both the energy

consumption and the quality of the final product

depend on technical–technological parameters of

granulation or briquetting processes. Most

essentially these parameters include the kind and

moisture content of processed material,

temperature of the process, working surface,

length, diameter, and geometrical shape of the die

holes (Laskowskiet al., 1994).

The value of the proximate and ultimate analysis is

that it identifies the fuel value of the raw biomass

material, which provides an estimate of the ash

handling requirement and describes the burning

characteristics. Demirbas and Sahin (2004) stated

that for briquette quality control, the physical


576


parameters such as density, moisture content, and

compressive strength were found to be the best

indicators of additive quality and Several national

standards (DIN 51731, 1996, O NORM M7135,

2000 and ASAE 269.4, 1996) describe the particle

density of pellets and briquettes as a quality

indicator of densified fuels. The factors that mainly

influence the selection of raw materials are

moisture and ash contents, flow characteristics

and particle size. In view of the above facts an

attempt has been made to assess the feasibility of

agro-industrial wastes produced in the study area

for production of solid bio-fuel by proximate,

ultimate, SEM and FTIR analysis.

Plate 2: (A) Karnataka state map showing raw materials collected places and (B) Aerial views of Mysore

Paper Mill and Sugar Factory sludge disposal site.

2.0 Materials and Methods: Table 1 showing the raw materials used for the

production of briquettes and their respective

collected places (Plate 1(A)). There are two main

agro based industries located in Bhadravathi town;

Mysore Paper Mill and Sugar Factory, both having

single effluent treatment plant. In the primary

treatment unit an average of 3,907.2 tons per

month press dug is producing (Plate 1 (B)). The

agro-industrial wastes properties like moisture

content was determined after drying a sample at

105ºC according to ASTM D2016-25. To obtain the

ash content, a dried sample of 2g is burned at

800ºC during 5h according to ASTM D-5142. The

volatile matter was determined according to ISO

562/1974. It was measured by introducing a dry

sample of 1g into a crucible with a top at 950ºC for

5min. The fixed carbon (FC) was calculated by FC %

= 100 % - ash % - volatile matter % (Tabareset al.,

2000). The Gross Calorific Value (GCV) was

measured by a PARR 1261 bomb calorimeter in a

dry basis using samples of 1g according to the

standard method (ISO, 1976). In order to

understand the chemical functional groups

present in the agro-industrial wastes IR spectra

were run taken from the Fourier Transform

Infrared Spectroscopy (Perkin Elmer, FTIR1760).

The FT-IR spectra were run on agricultural waste (1

mg, 1 wt %) co-adding 64 scans at a resolution of 2

cm-1

. These spectra were scaled to 1 mg sample.

The morphological structure of the agricultural

waste was determined by using scanning electron

microscope (SEM, JEOL-JSM-6400, LF-Japan) at

25kv. The SEM analysis made to distinguish the

agricultural waste based on their morphological

structure and also it helped to predict their

agglomeration properties in order to be briquetted

(Blesa, et al., 2003).The results obtained from the

present study was evaluated using statistical

software SPSS, var.12.

B A


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Table 1: Agro-wastes and respective collection places

Agro-Waste Samples Place of Collection

Press Dug (PD) Mysore Paper Mill (MPM), Bhadravathi

Saw Mill Dust (SMD) Sri Veerabhadreshwara Saw Mill, Bhadravathi

Ground Nut Husk (GNS) Oil extraction unit of Challakeri, Chitradurgha District

Jatropa Seed Cake (JSC) Oil extraction unit of Hiriyuru, Chitradurgha District

Castor Seed Cake (CSC) Oil extraction unit of Hiriyuru, Chitradurgha District

Tamarind Fruit Shell (TFS) Challakeri, Chitradurgha District

3.0 Results and Discussion:

3.1 Characteristics of agricultural waste Result of proximate and ultimate analysis of agricultural waste is presented in the Table 2.

Table 2: Characteristics of agricultural residue (mean ± SD)

Parameters Moisture

Content (%)

Bulk

Density

(kg/m3)

Particle

Density

(kg/m3)

Volatile

Matter (%)

Ash

Content (%)

Fixed

Carbon (%)

Calorific

ValueMJ/kg

Sawmill Dust 1.84 ± 0.23 14.74 ± 0.48 98.22 ± 3.93 78.86 ± 1.15 1.75 ± 0.09 18.59 ± 1.33 17.55 ± 0.03

Ground Nut Shell 1.67 ± 0.05 12.60 ± 0.21 104.81 ± 4.27 79.50 ± 1.95 1.67 ± 0.21 18.35 ± 1.21 19.07 ± 0.01

Press Dug 2.75 ± 0.10 31.43 ± 1.47 98.26 ± 1.44 68.58 ± 1.81 12.28 ± 1.41 19.50 ± 0.82 15.06 ± 0.01

Tamarind Fruit Shell 2.96 ± 0.14 33.37 ± 1.92 115.24 ± 3.75 76.12 ± 2.18 3.27 ± 0.10 20.53 ± 1.25 15.10 ± 0.01

Caster Seed Cake 2.22 ± 0.06 63.19 ± 4.72 305.30 ± 8.79 90.21 ± 2.09 0.84 ± 0.06 8.99 ± 0.15 20.09 ± 0.01

Jatropha Seed Cake 1.99 ± 0.17 42.32 ± 1.83 216.33 ± 4.16 88.91 ± 3.72 0.95 ± 0.04 10.53 ± 0.54 18.87 ± 0.01

A. Proximate analysis

3.2 Moisture content (%) The lowest (mean ± SD) moisture content was

recorded in ground nut shell i.e., 1.67 ± 0.05 %

followed by sawmill dust (1.84 ± 0.23%), jatropha

seed cake (1.99 ± 0.17%), caster seed cake (2.22 ±

0.06%), press dug (2.75 ± 0.10%) and tamarind

fruit shell 2.96 ± 0.14% respectively was recorded.

High percentage of moisture in biomass materials

prevents their applications for thermo-chemical

conversion processes including combustion

similarly the water content has an influence on the

net calorific value, the combustion efficiency and

the temperature of combustion was noticed.

Increasing biomass materials moisture content

caused on decreasing the unit density of pellets

considerably even at high applied pressures. The

maximum pellet density of 1238.1 kg/m3 was

observed at the moisture of 5% in a prickly lettuce,

while it decreased to 926.5 kg/m3 in the moisture

content of 20% (Affan, 2009).

3.3 Bulk density (kg/m3)

The highest (mean ± SD) bulk density i.e., 63.19 ±

4.72 kg/m3 was recorded in caster seed cake

followed by jatropha seed cake (42.32 ± 1.83

kg/m3), tamarind fruit shell (33.37 ± 1.92 kg/m

3),

press dug (31.43 ± 1.47 kg/m3), sawmill dust (14.74

± 0.48 kg/m3) and the lowest 12.60 ± 0.21 kg/m

3

was observed in ground nut shell. A major

disadvantage of agricultural residues as a fuel is

their low bulk density, which makes handling

difficult, transport and storage expensive, and

gives rise to poor combustion properties (Grover

and Mishra, 1996). Briquettes have a certain bulk

density resulting in convenient stove automation

and dosing (Menind et al., 2012).

3.4 Particle density (kg/m3)

The highest (mean ± SD) particle density was

recorded in caster seed cake i.e., 305.30 ± 8.79

kg/m3 followed by jatropha seed cake (216.33 ±

4.16 kg/m3), tamarind fruit shell (115.24 ± 3.75

kg/m3), ground nut shell (104.81 ± 4.27 kg/m

3),

press dug (98.26 ± 1.44 kg/m3) and lowest 98.22 ±

3.93 kg/m3 was observed in sawmill dust. The

particle density influences the bulk density and the

combustion behaviour, as dense particles shows a

longer burnout time (Ingwald and Gerold, 2004).

3.5 Volatile matter (%) The highest (mean ± SD) volatile matter content

was witnessed in caster seed cake i.e., 90.21 ±

2.09% followed by jatropha seed cake (88.91 ±

3.72%), ground nut shell (79.50 ± 1.95%), sawmill

dust (78.86 ± 1.15%), tamarind fruit shell (76.12 ±

2.18%) and the lowest 68.58 ± 1.81% was found in

press dug.According to Van and Koppejan (2002)


578


the quantity of volatiles in biomass fuels is high

and usually varies between 76 and 86 wt % (db.) in

woody biomass. The higher proportion of volatiles

results the major part of the biomass fuel being

vaporised before homogeneous gas-phase

combustion reactions take place. The remaining

char undergoes heterogeneous combustion

reactions. Char oxidation lasts considerably longer

than the oxidation of combustible gases during the

combustion process. The amount of volatile

matter therefore strongly influences the thermal

decomposition and combustion behaviour of solid

fuels. Fuels with lower volatiles, or conversely a

very high fixed carbon value, such as coal, need to

be burnt on a grate as they take a long time to

burn out if they are not pulverized to a very small

size. A laboratory study of actual ash behaviour

from switchgrass (Panicumvirgatum) showed that

elements such as K, S, B, Na, and Cu were

volatilized from the ash at high temperatures

(Misra et al., 1993). Elements such as Ca, Mg, P,

Mn, Al, Fe and Si were retained even to high

temperatures (Steenari et al., 1999).

3.6 Ash content (%) The lowest (mean ± SD) 0.84 ± 0.06% of ash

content obtained from the caster seed cake

followed by jatropha seed cake (0.95 ± 0.04%),

ground nut shell (1.67 ± 0.21%), sawmill dust (1.75

± 0.09%), tamarind fruit shell (3.27 ± 0.10%) and

highest 12.28 ± 1.41% resulted from the press

dug.One particular problem that is encountered

during thermal processes of biomass is the

deposition and agglomeration caused from

minerals in ash melts. Baxter (1993) stated: “Ash

behaviour of agro-waste during thermochemical

conversion is one of the most important matters

to be studied”. The minerals present with the

feedstock, when subjected to high temperature

and certain conditions, can agglomerate and

deposit inside the thermal device leading to slag

formation, fouling and bed agglomeration.

Inorganic constituents, such as organically bound

cations, inorganic salts and minerals make up the

ash present in or on the surface of biomass

(Arvelakis and Koukios, 2002). Ashes are usually

formed of CaO, K2O, Na2O, MgO, SiO2, Fe2O3, P2O5,

SO3 and Cl (Reed et al., 1980). The ash content of

agricultural waste affects its slagging behavior

together with the operating temperature and

mineral composition of ash.

3.7 Fixed carbon (%) The lowest (mean ± SD) fixed carbon recorded in

caster seed cake i.e.,8.99 ± 0.15% followed by

jatropha seed cake (10.53 ± 0.54%), ground nut

shell (18.35 ± 1.21%), sawmill dust (18.59 ±

1.33%), press dug (19.50 ± 0.82%) and highest

20.53 ± 1.25% recorded in tamarind fruit shell. The

low fixed content making it tend to prolong

cooking time by its low heat release (bake-oven

effect) (Onchieku et al.,). It also reduced the

calorific energy of the briquettes by causing what

is called fuel-saving effect. The higher the fixed

carbon content the better the charcoal produced

because the corresponding calorific energy is

usually high (FAO, 1995).

3.8 SEM images The morphology structure of the agricultural waste

was determined by using scanning electron

microscope (JEOL-JSM-6400, LF-Japan) at 25kv

(Plate 1). The morphological structure of the

sawmill dust showed uniform short fibrous and

coarser structure. Whereas, groundnut shell image

showed the masses of loose spongy lignocellulosic

structures. Further press dug image indicated long

uniform fibrous lignocellulosic structure. Whereas

castor and jatropha seed cakes images showed

large and small dens granulated structures

respectively. The tamarind fruit shell image

illustrates large and dense structures. The

morphology structure of the agricultural waste

studies helps to predict their agglomeration

properties in order to be briquetted. Blesaet al.

(2003) reported that typical fibrous texture of

sawdust could favor the coal–biomass

agglomeration and, as a consequence, it would

produce the increase of IRI and compression

strength.

B. Ultimate analysis

3.9 Calorific value (MJ/kg)

Heat value or calorific value determines the energy

content of a fuel. It is the property of biomass fuel

that depends on its chemical composition and

moisture content. The calorific value of caster seed

cake resulted highest i.e., 20.09 ± 0.01 MJ/kg

followed by ground nut shell 19.07 ± 0.01 MJ/kg,

jatropha seed cake 18.87 ± 0.01 MJ/kg, sawmill

dust 17.55 ± 0.03 MJ/kg, tamarind fruit shell 15.10

± 0.01 and lowest observed in press dug i.e., 15.06

± 0.01 MJ/kg (Table 2). The calorific value can be

used to calculate the competitiveness of a

processed fuel in a given market situation. There is

a range of other factors, such as ease of handling,

burning characteristics etc., which also influence

the market value, but calorific value is probably

the most important factor and should be

recognized when selecting the raw material input. The most important fuel property is its calorific or

heat value (Aina et al., 2009).


579


Plate 2: SEM images of agro-waste


580


3.10 FTIR spectra analysis The presence of chemical groups influences the

calorific value, binding properties and ash content

of the agricultural waste (Akowuah et al., 2012).

Fig. 1 shows theFT-IR spectra analysis of raw

materials. The analysis detected alkyne C-H bend

at around 670 cm-1

, Si-o stretch found around 670

cm-1

, sulfur compounds S=O stretch establish

around 1162 cm-1

, aliphatic amines C-N stretch

present around 1244 cm-1

, methylene C-H bend

approximately 1458 cm-1

range, secondary amides

N-H bend found near 1458 cm-1

, alkene C-C

symmetric stretch detected around 1657 cm-1

range, methylne symmetric C-H stretch present

around 2927 cm-1

range, methylne anti-symmetric

C-H stretch found around 2928 cm-1

, amines N-H

stretch established around 3419 cm-1

and

urethanes amides stretch were detected around

1734 cm-1

range. These chemical groups were

commonly found in all the samples of briquettes

raw materials. But intensities of chemical groups

were found to be varied from each other.

Fig. 1. FT-IR spectra of the briquettes raw

materials

4.0 Conclusion: Sawmill dust had good properties like lees

moisture content, bulk density, particle density,

ash content, fixed carbon, moderate calorific value

and uniform short fibrous and coarser structure. It

can be alone used for the production of briquettes

and it will give good mechanical as well

combustion properties to briquettes. Ground nut

shell also had good properties like lees moisture

content, particle density, ash content, fixed

carbon, high calorific value but very less bulk

density and it has loose spongy lignocellulosic

structures. Press dug and tamarind fruit shells

have high ash content and fixed carbon and very

less calorific value and volatile matter but it has

long uniform fibrous lignocellulosic structure i.e

they give good mechanical property but fails in

combustion properties. Caster Seed Cake and

Jatropha Seed Cake have good combustion

properties but they have high bulk density, particle

density with large and dense structured particles

hence they required high energy to compress and

they produce poor mechanical strength briquettes.

With this study suggests that the combination of

raw materials used during production of bio-

briquettes may give better mechanical strength as

well as combustionproperties then the single raw

material used.

5.0 Acknowledgement: The authors are grateful to the Kuvempu

University and Department of Biotechnology, New

Delhi for providing the facilities and financial

support to carry out this work.

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